EP3995484A1 - Heat exchange system and diester-based composition preparation system comprising same - Google Patents

Heat exchange system and diester-based composition preparation system comprising same Download PDF

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Publication number
EP3995484A1
EP3995484A1 EP20835106.4A EP20835106A EP3995484A1 EP 3995484 A1 EP3995484 A1 EP 3995484A1 EP 20835106 A EP20835106 A EP 20835106A EP 3995484 A1 EP3995484 A1 EP 3995484A1
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EP
European Patent Office
Prior art keywords
temperature stream
high temperature
stream
low temperature
heat exchanging
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
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EP20835106.4A
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German (de)
French (fr)
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EP3995484A4 (en
EP3995484B1 (en
Inventor
Jae Hun Jeong
Sung Kyu Lee
Yeon Uk Choo
Hyoung JUN
Chan Hyu JIN
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LG Chem Ltd
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LG Chem Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/06—Flash distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/245—Stationary reactors without moving elements inside placed in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00495—Means for heating or cooling the reaction vessels
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a heat exchange system which is designed for allowing efficient heat exchange and a preparation system of a diester-based composition comprising the heat exchange system.
  • Phthalate-based plasticizers account for 92% of the world plasticizer market until the 20th century (see Mustafizur Rahman and Christopher S. Brazel "The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges" Progress in Polymer Science 2004, 29, 1223-1248 ) and are added as additives for mostly imparting polyvinyl chloride (hereinafter, will referred to as PVC) with flexibility, durability, cold resistance, etc., and reducing the viscosity during melting to improve processability to PVC in various contents and widely used for intimate relation in real life and inevitable direct contact with the human body from hard products such as hard pipes to soft products which may be used in food package materials and blood bags, flooring materials, etc., because of the softness and well-stretching properties thereof when compared to any other materials.
  • PVC polyvinyl chloride
  • phthalate-based plasticizers particularly, di(2-ethylhexyl) phthalate
  • many researchers have proceeded research on developing a novel non-phthalate-based replaceable plasticizers excluding anhydrous phthalic acid which has been used for preparing di(2-ethylhexyl) phthalate
  • developing phthalate-based plasticizers which may replace di(2-ethylhexyl) phthalate, which may, though phthalate-based, suppress the release of the plasticizer and be used industrially
  • release-suppressing technique by which the release of phthalate-based plasticizers may be suppressed to markedly reduce the harmfulness to the human body and which may coincide with environmental standards.
  • a batch type process is applied in most industrial sites, and an invention on a gas-liquid separation system for refluxing unreacted materials in a reactor and effective removal of by-products in a batch type process ( Korean Patent Publication No. 10-2019-0027622 ), an invention on a system in which equipment for first direct esterification reaction and equipment for second trans esterification reaction are combined for the simplification of equipment for a batch type process ( Korean Patent Publication No. 10-2019-0027623 ), etc. have been disclosed.
  • Such inventions employ a batch type process, and there are limitations on the improvement of refluxing amount or steam amount, productivity is very low, and there are limitations on technique applicable for improvement.
  • the present invention provides a heat exchange system which may be applied to a continuously operated preparation system of a diester-based composition and may save steam and a cooling agent used in a whole process by optimizing heat exchange between streams having different temperatures, and a preparation system of a diester-based composition comprising the heat exchange system.
  • the present invention provides, in a preparation system of a diester-based composition, a heat exchange system comprising a heat exchange part composed for heat exchange between one or more high temperature streams selected from the group consisting of a first high temperature stream discharged from a second purification part and injected into a mixed alcohol tank, a second high temperature stream discharged from a preliminary purification part and injected into a first alcohol tank, a third high temperature stream discharged from a trans reaction part and injected into a second washing part, a fourth high temperature stream discharged from the preliminary purification part and injected into a first washing part, and a fifth high temperature stream discharged from a separation part and injected into at least one of the first alcohol tank and a reaction part, and one or more low temperature streams selected from the group consisting of a first low temperature stream discharged from the second washing part and injected into the second purification part, a second low temperature stream discharged from a second alcohol tank and injected into the trans reaction part, a third low temperature stream discharged from the first washing part and
  • the used amounts of steam and a cooling agent in a whole process may be minimized.
  • Heat exchange systems were composed as shown in FIGS. 2 to 11 and regarded as Examples 1 to 10, respectively, and a case of a process for the same diester-based preparation without a heat exchange system was regarded as Comparative Example.
  • the used amounts of total energy, the used amounts of cooling water, the used amounts of steam and heat exchange ratios in Examples 1 to 10 were calculated based on the Comparative Example through a process simulation program, and are shown in Table 1 below.
  • the heat exchange ratio was calculated by dividing heat exchange calories by the used amount of total energy.
  • Example 1 Used amount of energy (%) Used amount of cooling water (%) Used amount of steam (%) Heat exchange ratio (%) Comparative Example 100 100 100 0 Example 1 72 53 33 38 Example 2 74 56 38 34 Example 3 75 57 40 33 Example 4 74 56 38 34 Example 5 75 57 40 33 Example 6 74 56 38 34 Example 7 73 55 36 36 Example 8 75 57 40 33 Example 9 80 66 51 25 Example 10 79 65 50 26
  • high temperature stream refers to a stream having a relatively high temperature than other streams, particularly, a stream having a temperature of 150 to 250°C.
  • low temperature stream refers to a stream having a relatively low temperature than other streams, particularly, a stream having a temperature of 20 to 130°C.
  • dicarboxylic acid commonly refers to a compound having two carboxylic acid groups, particularly, one or more compounds selected from the group consisting of phthalic acid, terephthalic acid, isophthalic acid and cyclohexane dicarboxylic acid.
  • first alcohol and second alcohol refer to primary alcohols with 3 to 12 carbon atoms and include both linear type and branched type, and the first alcohol and the second alcohol are different alcohols from each other.
  • the heat exchange system of the present invention allows effective heat exchange between streams transported in a continuously operated preparation system of a diester-based composition. Accordingly, the continuously operated preparation system of a diester-based composition will be explained first, and then, the heat exchange system will be explained.
  • the basic preparation system of a diester-based composition which is applicable to the heat exchange system of the present invention will be explained below.
  • the following is for explaining an embodiment of the preparation system of a diester-based composition, applicable to the heat exchange system of the present invention, and it is obvious to apply the heat exchange system provided in the present invention even though some elements of the system are removed, added or modified within a range maintaining the basic structure of the preparation system of a diester-based composition explained below.
  • FIG. 1 An embodiment of the preparation system of a diester-based composition is shown in FIG. 1 , and the preparation system of a diester-based composition will be explained referring to FIG. 1 .
  • the preparation system of a diester-based composition includes a first alcohol tank 11, a second alcohol tank 12, a reaction part 21, a trans reaction part 22, a preliminary purification part 3, a first washing part 41, a second washing part 42, a first purification part 51, a second purification part 52, a mixed alcohol tank 61 and a separation part 62.
  • the first alcohol tank and the second alcohol tank contain a first alcohol and a second alcohol, corresponding to reaction raw materials.
  • the first alcohol is used for the esterification reaction with carboxylic acid
  • the second alcohol is used for the trans esterification reaction with an ester compound
  • a first alcohol stream 101 is transported to the reaction part
  • a second alcohol stream 102 is transported to the trans reaction part for the esterification reaction and the trans esterification reaction afterward.
  • the shape of the first alcohol tank and the second alcohol tank is not specifically limited, and any shape may be used as long as the first alcohol and the second alcohol may be stored without modification and may be easily transported.
  • the esterification reaction of the first alcohol and the dicarboxylic acid is performed.
  • the injection stream of the dicarboxylic acid is not shown in FIG. 1
  • the dicarboxylic acid may be directly injected into the reaction part, or may be mixed and injected into the first alcohol stream prior to the injection into the reaction part.
  • the reaction part may be provided with an internal space for the esterification reaction, and may be provided with a catalyst injection part for injecting a catalyst required for the reaction or a heating means for applying heat required for the esterification reaction. Common reaction parts used for the esterification reaction may be used without specific limitation.
  • the temperature at which the esterification reaction is mostly performed is a higher temperature than the boiling point of water which is the byproduct of the esterification reaction with an alcohol reaction raw material, the vaporization of water and alcohol is generated during the esterification reaction, and a sufficient conversion rate may not be accomplished.
  • an excessive amount of alcohol is generally injected than the alcohol equivalent required in practice.
  • unreacted alcohol is included in the reaction product in addition to an ester compound after finishing the reaction, and the first reaction product produced by the esterification reaction in the reaction part also includes an ester compound and unreacted first alcohol.
  • the first reaction product stream 211 is transported to the preliminary purification part 3 to remove the unreacted alcohol included in the reaction product.
  • the unreacted alcohol in the reaction product i.e., the unreacted first alcohol is removed.
  • the "removal” may be performed through known methods such as distillation, and any methods used for separating an ester compound and an alcohol compound may be applied without specific limitation.
  • the preliminary purification part may have a shape of a column, a distillation column, etc.
  • the unreacted first alcohol stream 303 removed from the preliminary purification part is transported to the first alcohol tank 11 to be used again as the reaction raw material.
  • the first reaction product (hereinafter, will be referred to as "purified product") from which the unreacted first alcohol is removed, is divided into different parts and injected to obtain two types of products.
  • One part 301 is transported to the first washing part to obtain a first diester-based composition, and the remainder 302 is transported to the trans reaction part to obtain a second diester-based composition.
  • the purified product 302 transported to the trans reaction part undergoes trans esterification reaction with the second alcohol 102 injected from the second alcohol tank to produce a second reaction product.
  • the trans reaction part may also be provided with an interior space, a catalyst injection part or a heating means as in the above-described reaction part, and any one known to be used for trans esterification reaction may be used without specific limitation.
  • the second reaction product may include the second alcohol in the reaction product, corresponding to a reaction raw material like the first reaction product, and may include the first alcohol produced through trans esterification reaction or un-removed in advance, considering the first alcohol is produced instead of water by trans esterification reaction.
  • the second reaction product stream 221 is transported to the second washing part to obtain a second diester-based composition afterward.
  • Both the first reaction product transported to the first washing part and the second reaction product 221 transported to the second washing part become the targets of neutralization and washing. Since an acidic catalyst is generally used for esterification reaction and trans esterification reaction, the neutralization and washing of the remaining catalyst is performed in the first washing part and the second washing part.
  • first neutralized product the temperature of the first reaction product
  • second neutralized product the second reaction product
  • the streams are transported to the first purification part and the second purification part to remove the first alcohol or a mixed alcohol, which may remain.
  • the first alcohol in the transporting first neutralized product stream 411 is removed, and a first diester-based composition 511 corresponding to a final product is obtained.
  • the mixed alcohol in the transporting second neutralized product stream 421 is removed, and a second diester-based composition 521 corresponding to a final product is obtained.
  • the removal of the alcohol in the first purification part and the second purification part may be performed through well-known methods such as distillation in the previous preliminary purification part, and any methods used for separating an ester compound and an alcohol compound may be applied without specific limitation.
  • the first purification part and the second purification part may have a shape of a flash drum, a column, a distillation column, etc.
  • the mixed alcohol tank 61 is for temporarily storing the mixed alcohol of the first alcohol and the second alcohol, and the shape or position thereof are not specifically limited as long as the modification of an alcohol is not induced like the first alcohol tank and the second alcohol tank.
  • the mixed alcohol stream 611 of the mixed alcohol tank is then injected into a separation part 62 and separated into a first alcohol stream 621 and a second alcohol stream 622, and then, the first alcohol stream is transported to at least one of the first alcohol tank and the reaction part, and the second alcohol stream is transported to the second alcohol tank.
  • the separation part is for separating the mixed alcohol and may preferably have a shape such as a distillation column capable of separating a mixture using a boiling point difference, because the first alcohol and the second alcohol have a boiling point difference.
  • the preparation system of a diester-based composition is continuously operated and is particularly suitable to apply a heat exchange system, because the flow rate of each stream is maintained constant. If the preparation system is discontinuously operated, the application of the heat exchange system of the present invention is not easy.
  • the present invention provides a heat exchange system which may be applied to the above-explained preparation system of a diester-based composition.
  • a heat exchange system which may be applied to the above-explained preparation system of a diester-based composition.
  • multiple high temperature streams having relatively high temperature and multiple low temperature streams having relatively low temperature are present.
  • a portion of the high temperature streams and a portion of the low temperature streams may require cooling or heating prior to undergoing a subsequent process.
  • a purified stream through a method such as distillation may have a relatively high temperature by heating during a distillation process, and the purified stream is required to be cooled prior to undergoing a subsequent process, because some vaporized components are required to be liquefied by reducing the temperature to store the purified stream in an apparatus such as a tank.
  • a stream inflowing into a washing part for washing which is carried out at a relatively low temperature is required to be cooled, and a stream discharged from the washing part may have a relatively low temperature, and since the stream is required to be heated through a process such as distillation in a purification step after washing, and accordingly, if the stream is partially heated prior to injecting to a purification step, energy consumed in the purification step may be reduced.
  • the heat exchange system of the present invention in the above-explained preparation system of a diester-based composition may include a heat exchange part composed for heat exchanging from each other between, one or more high temperature streams selected from the group consisting of a first high temperature stream discharged from the second purification part and injected into the mixed alcohol tank, a second high temperature stream discharged from the preliminary purification part and injected into the first alcohol tank, a third high temperature stream discharged from the trans reaction part and injected into the second washing part, a fourth high temperature stream discharged from the preliminary purification part and injected into the first washing part, and a fifth high temperature stream discharged from the separation part and injected into at least one of the first alcohol tank and the reaction part, and one or more low temperature streams selected from the group consisting of a first low temperature stream discharged from the second washing part and injected into the second purification part, a second low temperature stream discharged from the second alcohol tank and injected into the trans reaction part, a third low temperature stream discharged from the first washing part and injected
  • the high temperature stream which is a target for heat exchanging includes five different high temperature streams of first to fifth high temperature streams.
  • the first high temperature stream is a stream discharged from the second purification part and injected into the mixed alcohol tank, and a mixed alcohol removed through a process such as distillation in the second purification part may have a gas or liquid phase.
  • the alcohol present in a gas has a large volume, is difficult to store directly in the mixed alcohol tank and is required to be liquefied, and for the safe storage of the liquid phase, the temperature is required to be reduced further.
  • the second high temperature stream is a stream discharged from the preliminary purification part and injected into the first alcohol tank, and like the case of the first high temperature stream, the first alcohol removed through a process such as distillation may have a gas or liquid phase and is required to be cooled.
  • the third high temperature stream is a stream discharged from the trans reaction part and injected into the second washing part. Since trans esterification reaction performed in the trans reaction part is performed at a relatively high temperature, the stream discharged therefrom and injected into the second washing part also has a high temperature. The stream is then cooled in a neutralization and washing processes in the second washing part, and if a cooling process is performed in advance, energy amount consumed in the second washing part may be reduced. Accordingly, the third high temperature stream is required to be cooled.
  • the fourth high temperature stream is a stream discharged from the preliminary purification part and injected into the first washing part. Like the second high temperature stream, the fourth high temperature stream is discharged from the preliminary purification part and has a high temperature, and is required to be cooled because cooling is performed in subsequent neutralization and washing processes like the third high temperature stream.
  • the fifth high temperature stream is a stream discharged from the separation part and injected into at least one of the first alcohol tank and the reaction part.
  • the separation of the mixed alcohol in the separation part may be accompanied with heating, and accordingly, the stream to be separated in the separation part and injected into at least one of the first alcohol tank and the reaction part is a high temperature stream. Accordingly, the alcohol is required to be cooled to inject into the first alcohol tank and the reactor, and the fifth high temperature stream is required to be cooled.
  • the temperature of the first to fifth high temperature streams may be changed according to the operation conditions of a process, or specific selection of dicarboxylic acid, first alcohol and second alcohol, which are reaction raw materials, but may be included in a range of about 150 to 250°C.
  • the low temperature stream which is a target for heat exchanging includes four different low temperature streams of first to fourth low temperature streams.
  • the first low temperature stream is a stream discharged from the second washing part and injected into the second purification part.
  • the stream undergone a washing process has a relatively low temperature and is required to be heated because a mixed alcohol in the stream is required to be heated for separation in a subsequent purification part.
  • the second low temperature stream is a stream discharged from the second alcohol tank and injected into the trans reaction part. Since the second alcohol stored in the second alcohol tank is present in a liquid phase, this stream has a relatively low temperature and is required to be heated because reaction raw materials are required to be heated for the reaction in a subsequent trans reaction part.
  • the third low temperature stream is a stream discharged from the first washing part and injected into the first purification part, and like the first low temperature stream, has a low temperature through the washing process and is required to be heated for separating the first alcohol in the stream afterward.
  • the fourth low temperature stream is a stream discharged from the mixed alcohol tank and injected into the separation part.
  • the mixed alcohol stored in the mixed alcohol tank is present in a liquid state, and this stream has a relatively low temperature and is required to be heated because heating is required for separating the first alcohol and the second alcohol in a subsequent separation part.
  • the temperature of the first to fourth low temperature streams may be changed according to the operation conditions of a process, or specific selection of dicarboxylic acid, first alcohol and second alcohol, which are reaction raw materials, but may be included in a range of about 20 to 130°C.
  • the heat exchange part included in the heat exchange system of the present invention is configured to exchange heat between one or more high temperature streams selected from the first to fifth high temperature streams and one or more low temperature streams selected from the first to fourth low temperature streams.
  • the heat exchange part includes one heat exchanging apparatus, but may include multiple heat exchanging apparatuses. In terms of maximizing the energy efficiency of a whole process, multiple heat exchanging apparatuses are preferable. If the multiple heat exchanging apparatuses are provided, the heat exchange part means a heat exchanging system itself including all the multiple heat exchanging apparatuses, and the type, shape, etc. of each heat exchanging apparatus are not specifically limited only if the object of heat exchanging may be accomplished, and the position thereof is not additionally limited as long as the position allows smooth heat exchange of the high temperature streams and the low temperature streams, which are targets for heat exchanging.
  • the heat exchange system of the present invention may be configured as shown in FIGS. 2 to 11 .
  • the heat exchange systems shown in FIGS. 2 to 11 illustrate embodiments of the heat exchange system of the present invention, respectively, and show only streams which are targets for heat exchanging in the preparation system of a diester-based composition of FIG. 1 , and the indication of remaining streams is omitted.
  • a heat exchanger performing heat exchanging is indicated by HX.
  • FIGS. 2 to 11 of the present disclosure illustrate embodiments of the heat exchange system of the present invention, and it is obvious that the scope of the present invention is not limited to the scope of FIGS. 2 to 11 .
  • the heat exchange part is composed for heat exchanging the first high temperature stream with the third low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the second low temperature stream, and heat exchanging the fifth high temperature stream with the fourth low temperature stream.
  • the heat exchange part is composed for heat exchanging the first high temperature stream with the second low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the third low temperature stream, and heat exchanging the fifth high temperature stream with the fourth low temperature stream.
  • the heat exchange part is composed for heat exchanging the first high temperature stream with the second low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the fourth low temperature stream, and heat exchanging the fifth high temperature stream with the third low temperature stream.
  • the heat exchange part is composed for heat exchanging the first high temperature stream with the second low temperature stream and the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, and heat exchanging the fourth high temperature stream with the third low temperature stream.
  • the heat exchange part is composed for heat exchanging the first high temperature stream with the second low temperature stream and the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, and heat exchanging the fifth high temperature stream with the third low temperature stream.
  • the heat exchange part is composed for heat exchanging the first high temperature stream with the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the third low temperature stream, and heat exchanging the fifth high temperature stream with the second low temperature stream.
  • the heat exchange part is composed for heat exchanging the first high temperature stream with the third low temperature stream and the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the third low temperature stream, and heat exchanging the fifth high temperature stream with the second low temperature stream.
  • the heat exchange part is composed for heat exchanging the first high temperature stream with the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the second low temperature stream, and heat exchanging the fifth high temperature stream with the third low temperature stream.
  • the heat exchange part is composed for heat exchanging the first high temperature stream and the second high temperature stream with the first low temperature stream, heat exchanging the third high temperature stream with the fourth low temperature stream, heat exchanging the fourth high temperature stream with the second low temperature stream, and heat exchanging the fifth high temperature stream with the third low temperature stream.
  • the heat exchange part is composed for heat exchanging the first high temperature stream and the second high temperature stream with the first low temperature stream, heat exchanging the third high temperature stream with the fourth low temperature stream, heat exchanging the fourth high temperature stream with the third low temperature stream, and heat exchanging the fifth high temperature stream with the second low temperature stream.

Abstract

The present invention relates to a heat exchange system which is capable of saving energy consumed in a whole process by exchanging heat of different streams from each other, included in a continuous preparation system of a diester-based composition.

Description

    TECHNICAL FIELD [Cross-reference to Related Applications]
  • The present application claims the benefit of priority based on Korean Patent Application No. 10-2019-0080463, filed on July 4, 2019 , the entire contents of which are incorporated herein by reference.
    • [Technical Field]
  • The present invention relates to a heat exchange system which is designed for allowing efficient heat exchange and a preparation system of a diester-based composition comprising the heat exchange system.
    • BACKGROUND ART
  • Phthalate-based plasticizers account for 92% of the world plasticizer market until the 20th century (see Mustafizur Rahman and Christopher S. Brazel "The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges" Progress in Polymer Science 2004, 29, 1223-1248) and are added as additives for mostly imparting polyvinyl chloride (hereinafter, will referred to as PVC) with flexibility, durability, cold resistance, etc., and reducing the viscosity during melting to improve processability to PVC in various contents and widely used for intimate relation in real life and inevitable direct contact with the human body from hard products such as hard pipes to soft products which may be used in food package materials and blood bags, flooring materials, etc., because of the softness and well-stretching properties thereof when compared to any other materials.
  • However, despite the compatibility with PVC and excellent softness imparting properties of the phthalate-based plasticizers, recently, in case of using the PVC products containing the phthalate-based plasticizers in real life, controversy over harmfulness has been suggested in that the phthalate-based plasticizers might be released little by little out of the products and act as suspected endocrine disruptors (environmental hormone) and a carcinogen with a heavy metal level (see N. R. Janjua et al. "Systemic Uptake of Diethyl Phthalate, Dibutyl Phthalate, and Butyl Paraben Following Whole-body Topical Application and Reproductive and Thyroid Hormone Levels in Humans" Environmental Science and Technology 2007, 41, 5564-5570). Particularly, after a report has been announced in 1960s in America that the most used di-(2-ethylhexyl) phthalate (DEHP) among phthalate-based plasticizers is released out of PVC products, with added interest on environmental hormone in 1990s, various studies on the harmfulness of phthalate plasticizers to the human body and worldwide environmental regulations have been started.
  • Accordingly, in order to cope with environmental hormone issues and environmental regulations due to the release of phthalate-based plasticizers, particularly, di(2-ethylhexyl) phthalate, many researchers have proceeded research on developing a novel non-phthalate-based replaceable plasticizers excluding anhydrous phthalic acid which has been used for preparing di(2-ethylhexyl) phthalate, developing phthalate-based plasticizers which may replace di(2-ethylhexyl) phthalate, which may, though phthalate-based, suppress the release of the plasticizer and be used industrially, and developing release-suppressing technique by which the release of phthalate-based plasticizers may be suppressed to markedly reduce the harmfulness to the human body and which may coincide with environmental standards.
  • As described above, the development of materials which are free from environmental issues and replaceable with di(2-ethylhexyl) phthalate which is a diester-based plasticizer and has the existing environmental issues, is actively being conducted, research on developing diester-based plasticizers having excellent physical properties and research on equipment for preparing such plasticizers are actively being conducted, and the design for more efficient, economic and simple processes in view of process design is required.
  • Meanwhile, in a process for preparing the diester-based plasticizer above, a batch type process is applied in most industrial sites, and an invention on a gas-liquid separation system for refluxing unreacted materials in a reactor and effective removal of by-products in a batch type process ( Korean Patent Publication No. 10-2019-0027622 ), an invention on a system in which equipment for first direct esterification reaction and equipment for second trans esterification reaction are combined for the simplification of equipment for a batch type process ( Korean Patent Publication No. 10-2019-0027623 ), etc. have been disclosed. However, such inventions employ a batch type process, and there are limitations on the improvement of refluxing amount or steam amount, productivity is very low, and there are limitations on technique applicable for improvement.
  • In addition, as a continuous process, an invention relating to a process composing a reaction part through connecting two or more reactors in series ( Korean Registered Patent Publication No. 10-1663586 ) has been disclosed, but only with the control of the reaction temperature of continuously connected reactors, the improvement of overall processability is limited.
    • Prior Art Documents Patent Documents
    • (Patent Document 1) Korean Patent Publication No. 10-2019-0027622
    • (Patent Document 2) Korean Patent Publication No. 10-2019-0027623
    • (Patent Document 3) Korean Registered Patent Publication No. 10-1663586
    Non-patent documents
    • DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM
  • The present invention provides a heat exchange system which may be applied to a continuously operated preparation system of a diester-based composition and may save steam and a cooling agent used in a whole process by optimizing heat exchange between streams having different temperatures, and a preparation system of a diester-based composition comprising the heat exchange system.
    • TECHNICAL SOLUTION
  • The present invention provides, in a preparation system of a diester-based composition, a heat exchange system comprising a heat exchange part composed for heat exchange between one or more high temperature streams selected from the group consisting of a first high temperature stream discharged from a second purification part and injected into a mixed alcohol tank, a second high temperature stream discharged from a preliminary purification part and injected into a first alcohol tank, a third high temperature stream discharged from a trans reaction part and injected into a second washing part, a fourth high temperature stream discharged from the preliminary purification part and injected into a first washing part, and a fifth high temperature stream discharged from a separation part and injected into at least one of the first alcohol tank and a reaction part, and one or more low temperature streams selected from the group consisting of a first low temperature stream discharged from the second washing part and injected into the second purification part, a second low temperature stream discharged from a second alcohol tank and injected into the trans reaction part, a third low temperature stream discharged from the first washing part and injected into a first purification part, and a fourth low temperature stream discharged from the mixed alcohol tank and injected into the separation part.
    • ADVANTAGEOUS EFFECTS
  • In the heat exchange system of the present invention, by pairing up multiple high temperature streams having relatively higher temperature and multiple low temperature streams having relatively lower temperature and allowing heat exchange, the used amounts of steam and a cooling agent in a whole process may be minimized.
    • BRIEF DESCRIPTION OF THE DRAWINGS
    • FIG. 1 illustrates the conventional continuous operating preparation system of a diester-based composition, to which the heat exchange system of the present invention is applicable.
    • FIGS. 2 to 11 illustrate preparation systems of a diester-based composition, to which the heat exchange systems according to Examples 1 to 10 of the present invention are applied, respectively.
    BEST MODE FOR CARRYING OUT THE INVENTION
  • Hereinafter, preferred embodiments will be suggested to assist the understanding of the present invention. However, the embodiments are only for illustrating the present invention and do not limit the scope of the present invention.
    • Examples 1 to 10
  • Heat exchange systems were composed as shown in FIGS. 2 to 11 and regarded as Examples 1 to 10, respectively, and a case of a process for the same diester-based preparation without a heat exchange system was regarded as Comparative Example. The used amounts of total energy, the used amounts of cooling water, the used amounts of steam and heat exchange ratios in Examples 1 to 10 were calculated based on the Comparative Example through a process simulation program, and are shown in Table 1 below. The heat exchange ratio was calculated by dividing heat exchange calories by the used amount of total energy. [Table 1]
    Used amount of energy (%) Used amount of cooling water (%) Used amount of steam (%) Heat exchange ratio (%)
    Comparative Example 100 100 100 0
    Example 1 72 53 33 38
    Example 2 74 56 38 34
    Example 3 75 57 40 33
    Example 4 74 56 38 34
    Example 5 75 57 40 33
    Example 6 74 56 38 34
    Example 7 73 55 36 36
    Example 8 75 57 40 33
    Example 9 80 66 51 25
    Example 10 79 65 50 26
  • It was confirmed that all Examples 1 to 10 saved energy by at least 20% when compared to Comparative Example, the used amount of cooling water was saved to maximum half, and the used amount of steam was saved to maximum 1/3. Accordingly, it was confirmed that the heat exchange system of the present invention may provide excellent energy efficiency.
    • MODE FOR CARRYING OUT THE INVENTION
  • Hereinafter, the present invention will be explained in more detail.
  • It will be understood that words or terms used in the specification and claims shall not be interpreted as the meaning defined in commonly used dictionaries. It will be further understood that the words or terms should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the technical idea of the invention, based on the principle that an inventor may properly define the meaning of the words or terms to best explain the invention.
  • In the present invention, "high temperature stream" refers to a stream having a relatively high temperature than other streams, particularly, a stream having a temperature of 150 to 250°C.
  • In the present invention, "low temperature stream" refers to a stream having a relatively low temperature than other streams, particularly, a stream having a temperature of 20 to 130°C.
  • In the present invention, "dicarboxylic acid" commonly refers to a compound having two carboxylic acid groups, particularly, one or more compounds selected from the group consisting of phthalic acid, terephthalic acid, isophthalic acid and cyclohexane dicarboxylic acid.
  • In the present invention, "first alcohol" and "second alcohol" refer to primary alcohols with 3 to 12 carbon atoms and include both linear type and branched type, and the first alcohol and the second alcohol are different alcohols from each other.
  • The heat exchange system of the present invention allows effective heat exchange between streams transported in a continuously operated preparation system of a diester-based composition. Accordingly, the continuously operated preparation system of a diester-based composition will be explained first, and then, the heat exchange system will be explained.
    • Preparation system of diester-based composition
  • The basic preparation system of a diester-based composition, which is applicable to the heat exchange system of the present invention will be explained below. The following is for explaining an embodiment of the preparation system of a diester-based composition, applicable to the heat exchange system of the present invention, and it is obvious to apply the heat exchange system provided in the present invention even though some elements of the system are removed, added or modified within a range maintaining the basic structure of the preparation system of a diester-based composition explained below.
  • An embodiment of the preparation system of a diester-based composition is shown in FIG. 1, and the preparation system of a diester-based composition will be explained referring to FIG. 1.
  • The preparation system of a diester-based composition includes a first alcohol tank 11, a second alcohol tank 12, a reaction part 21, a trans reaction part 22, a preliminary purification part 3, a first washing part 41, a second washing part 42, a first purification part 51, a second purification part 52, a mixed alcohol tank 61 and a separation part 62.
  • The first alcohol tank and the second alcohol tank contain a first alcohol and a second alcohol, corresponding to reaction raw materials. The first alcohol is used for the esterification reaction with carboxylic acid, and the second alcohol is used for the trans esterification reaction with an ester compound, a first alcohol stream 101 is transported to the reaction part, and a second alcohol stream 102 is transported to the trans reaction part for the esterification reaction and the trans esterification reaction afterward. The shape of the first alcohol tank and the second alcohol tank is not specifically limited, and any shape may be used as long as the first alcohol and the second alcohol may be stored without modification and may be easily transported.
  • In the reaction part 21, the esterification reaction of the first alcohol and the dicarboxylic acid is performed. Though the injection stream of the dicarboxylic acid is not shown in FIG. 1, the dicarboxylic acid may be directly injected into the reaction part, or may be mixed and injected into the first alcohol stream prior to the injection into the reaction part. The reaction part may be provided with an internal space for the esterification reaction, and may be provided with a catalyst injection part for injecting a catalyst required for the reaction or a heating means for applying heat required for the esterification reaction. Common reaction parts used for the esterification reaction may be used without specific limitation.
  • Meanwhile, since the temperature at which the esterification reaction is mostly performed is a higher temperature than the boiling point of water which is the byproduct of the esterification reaction with an alcohol reaction raw material, the vaporization of water and alcohol is generated during the esterification reaction, and a sufficient conversion rate may not be accomplished. In order to prevent this defect, an excessive amount of alcohol is generally injected than the alcohol equivalent required in practice. Accordingly, unreacted alcohol is included in the reaction product in addition to an ester compound after finishing the reaction, and the first reaction product produced by the esterification reaction in the reaction part also includes an ester compound and unreacted first alcohol. The first reaction product stream 211 is transported to the preliminary purification part 3 to remove the unreacted alcohol included in the reaction product.
  • In the preliminary purification part 3 to which the first reaction product is injected, the unreacted alcohol in the reaction product, i.e., the unreacted first alcohol is removed. The "removal" may be performed through known methods such as distillation, and any methods used for separating an ester compound and an alcohol compound may be applied without specific limitation. For example, the preliminary purification part may have a shape of a column, a distillation column, etc. The unreacted first alcohol stream 303 removed from the preliminary purification part is transported to the first alcohol tank 11 to be used again as the reaction raw material. Meanwhile, the first reaction product (hereinafter, will be referred to as "purified product") from which the unreacted first alcohol is removed, is divided into different parts and injected to obtain two types of products. One part 301 is transported to the first washing part to obtain a first diester-based composition, and the remainder 302 is transported to the trans reaction part to obtain a second diester-based composition.
  • The purified product 302 transported to the trans reaction part undergoes trans esterification reaction with the second alcohol 102 injected from the second alcohol tank to produce a second reaction product. The trans reaction part may also be provided with an interior space, a catalyst injection part or a heating means as in the above-described reaction part, and any one known to be used for trans esterification reaction may be used without specific limitation.
  • Meanwhile, the second reaction product may include the second alcohol in the reaction product, corresponding to a reaction raw material like the first reaction product, and may include the first alcohol produced through trans esterification reaction or un-removed in advance, considering the first alcohol is produced instead of water by trans esterification reaction. The second reaction product stream 221 is transported to the second washing part to obtain a second diester-based composition afterward.
  • Both the first reaction product transported to the first washing part and the second reaction product 221 transported to the second washing part become the targets of neutralization and washing. Since an acidic catalyst is generally used for esterification reaction and trans esterification reaction, the neutralization and washing of the remaining catalyst is performed in the first washing part and the second washing part. After performing the neutralization and washing, the temperature of the first reaction product (hereinafter, will be referred to as "first neutralized product") and the second reaction product (hereinafter, will be referred to as "second neutralized product") streams is lowered due to a washing step, and the streams are transported to the first purification part and the second purification part to remove the first alcohol or a mixed alcohol, which may remain.
  • In the first purification part, the first alcohol in the transporting first neutralized product stream 411 is removed, and a first diester-based composition 511 corresponding to a final product is obtained. In addition, in the second purification part, the mixed alcohol in the transporting second neutralized product stream 421 is removed, and a second diester-based composition 521 corresponding to a final product is obtained. The removal of the alcohol in the first purification part and the second purification part may be performed through well-known methods such as distillation in the previous preliminary purification part, and any methods used for separating an ester compound and an alcohol compound may be applied without specific limitation. For example, the first purification part and the second purification part may have a shape of a flash drum, a column, a distillation column, etc.
  • Meanwhile, the first alcohol 512 removed in the first purification part and the mixed alcohol 522 removed in the second purification part are transported to the mixed alcohol tank 61. The mixed alcohol tank 61 is for temporarily storing the mixed alcohol of the first alcohol and the second alcohol, and the shape or position thereof are not specifically limited as long as the modification of an alcohol is not induced like the first alcohol tank and the second alcohol tank. The mixed alcohol stream 611 of the mixed alcohol tank is then injected into a separation part 62 and separated into a first alcohol stream 621 and a second alcohol stream 622, and then, the first alcohol stream is transported to at least one of the first alcohol tank and the reaction part, and the second alcohol stream is transported to the second alcohol tank.
  • The separation part is for separating the mixed alcohol and may preferably have a shape such as a distillation column capable of separating a mixture using a boiling point difference, because the first alcohol and the second alcohol have a boiling point difference.
  • The preparation system of a diester-based composition is continuously operated and is particularly suitable to apply a heat exchange system, because the flow rate of each stream is maintained constant. If the preparation system is discontinuously operated, the application of the heat exchange system of the present invention is not easy.
    • Heat exchange system
  • The present invention provides a heat exchange system which may be applied to the above-explained preparation system of a diester-based composition. In the continuous preparation process of a diester-based composition, multiple high temperature streams having relatively high temperature and multiple low temperature streams having relatively low temperature are present. In addition, a portion of the high temperature streams and a portion of the low temperature streams may require cooling or heating prior to undergoing a subsequent process.
  • For example, a purified stream through a method such as distillation may have a relatively high temperature by heating during a distillation process, and the purified stream is required to be cooled prior to undergoing a subsequent process, because some vaporized components are required to be liquefied by reducing the temperature to store the purified stream in an apparatus such as a tank. In addition, a stream inflowing into a washing part for washing which is carried out at a relatively low temperature is required to be cooled, and a stream discharged from the washing part may have a relatively low temperature, and since the stream is required to be heated through a process such as distillation in a purification step after washing, and accordingly, if the stream is partially heated prior to injecting to a purification step, energy consumed in the purification step may be reduced.
  • As described above, in the continuous preparation system of a diester-based composition, multiple high temperature streams and low temperature streams, requiring cooling or heating are present, and the inventors of the present invention found that energy consumed for cooling and heating each stream in a subsequent step could be saved by designing a heat exchange part for exchanging heat between the high temperature streams and the low temperature streams, and completed the present invention.
  • Particularly, the heat exchange system of the present invention in the above-explained preparation system of a diester-based composition may include a heat exchange part composed for heat exchanging from each other between, one or more high temperature streams selected from the group consisting of a first high temperature stream discharged from the second purification part and injected into the mixed alcohol tank, a second high temperature stream discharged from the preliminary purification part and injected into the first alcohol tank, a third high temperature stream discharged from the trans reaction part and injected into the second washing part, a fourth high temperature stream discharged from the preliminary purification part and injected into the first washing part, and a fifth high temperature stream discharged from the separation part and injected into at least one of the first alcohol tank and the reaction part, and one or more low temperature streams selected from the group consisting of a first low temperature stream discharged from the second washing part and injected into the second purification part, a second low temperature stream discharged from the second alcohol tank and injected into the trans reaction part, a third low temperature stream discharged from the first washing part and injected into the first purification part, and a fourth low temperature stream discharged from the mixed alcohol tank and injected into the separation part.
  • First, in the heat exchange system of the present invention, the high temperature stream which is a target for heat exchanging includes five different high temperature streams of first to fifth high temperature streams.
  • The first high temperature stream is a stream discharged from the second purification part and injected into the mixed alcohol tank, and a mixed alcohol removed through a process such as distillation in the second purification part may have a gas or liquid phase. The alcohol present in a gas has a large volume, is difficult to store directly in the mixed alcohol tank and is required to be liquefied, and for the safe storage of the liquid phase, the temperature is required to be reduced further.
  • The second high temperature stream is a stream discharged from the preliminary purification part and injected into the first alcohol tank, and like the case of the first high temperature stream, the first alcohol removed through a process such as distillation may have a gas or liquid phase and is required to be cooled.
  • The third high temperature stream is a stream discharged from the trans reaction part and injected into the second washing part. Since trans esterification reaction performed in the trans reaction part is performed at a relatively high temperature, the stream discharged therefrom and injected into the second washing part also has a high temperature. The stream is then cooled in a neutralization and washing processes in the second washing part, and if a cooling process is performed in advance, energy amount consumed in the second washing part may be reduced. Accordingly, the third high temperature stream is required to be cooled.
  • The fourth high temperature stream is a stream discharged from the preliminary purification part and injected into the first washing part. Like the second high temperature stream, the fourth high temperature stream is discharged from the preliminary purification part and has a high temperature, and is required to be cooled because cooling is performed in subsequent neutralization and washing processes like the third high temperature stream.
  • The fifth high temperature stream is a stream discharged from the separation part and injected into at least one of the first alcohol tank and the reaction part. The separation of the mixed alcohol in the separation part may be accompanied with heating, and accordingly, the stream to be separated in the separation part and injected into at least one of the first alcohol tank and the reaction part is a high temperature stream. Accordingly, the alcohol is required to be cooled to inject into the first alcohol tank and the reactor, and the fifth high temperature stream is required to be cooled.
  • The temperature of the first to fifth high temperature streams may be changed according to the operation conditions of a process, or specific selection of dicarboxylic acid, first alcohol and second alcohol, which are reaction raw materials, but may be included in a range of about 150 to 250°C.
  • In the heat exchange system of the present invention, the low temperature stream which is a target for heat exchanging includes four different low temperature streams of first to fourth low temperature streams.
  • The first low temperature stream is a stream discharged from the second washing part and injected into the second purification part. The stream undergone a washing process has a relatively low temperature and is required to be heated because a mixed alcohol in the stream is required to be heated for separation in a subsequent purification part.
  • The second low temperature stream is a stream discharged from the second alcohol tank and injected into the trans reaction part. Since the second alcohol stored in the second alcohol tank is present in a liquid phase, this stream has a relatively low temperature and is required to be heated because reaction raw materials are required to be heated for the reaction in a subsequent trans reaction part.
  • The third low temperature stream is a stream discharged from the first washing part and injected into the first purification part, and like the first low temperature stream, has a low temperature through the washing process and is required to be heated for separating the first alcohol in the stream afterward.
  • The fourth low temperature stream is a stream discharged from the mixed alcohol tank and injected into the separation part. Like the second low temperature stream, the mixed alcohol stored in the mixed alcohol tank is present in a liquid state, and this stream has a relatively low temperature and is required to be heated because heating is required for separating the first alcohol and the second alcohol in a subsequent separation part.
  • The temperature of the first to fourth low temperature streams may be changed according to the operation conditions of a process, or specific selection of dicarboxylic acid, first alcohol and second alcohol, which are reaction raw materials, but may be included in a range of about 20 to 130°C.
  • The heat exchange part included in the heat exchange system of the present invention is configured to exchange heat between one or more high temperature streams selected from the first to fifth high temperature streams and one or more low temperature streams selected from the first to fourth low temperature streams. The heat exchange part includes one heat exchanging apparatus, but may include multiple heat exchanging apparatuses. In terms of maximizing the energy efficiency of a whole process, multiple heat exchanging apparatuses are preferable. If the multiple heat exchanging apparatuses are provided, the heat exchange part means a heat exchanging system itself including all the multiple heat exchanging apparatuses, and the type, shape, etc. of each heat exchanging apparatus are not specifically limited only if the object of heat exchanging may be accomplished, and the position thereof is not additionally limited as long as the position allows smooth heat exchange of the high temperature streams and the low temperature streams, which are targets for heat exchanging.
  • More particularly, the heat exchange system of the present invention may be configured as shown in FIGS. 2 to 11. The heat exchange systems shown in FIGS. 2 to 11 illustrate embodiments of the heat exchange system of the present invention, respectively, and show only streams which are targets for heat exchanging in the preparation system of a diester-based composition of FIG. 1, and the indication of remaining streams is omitted. A heat exchanger performing heat exchanging is indicated by HX. FIGS. 2 to 11 of the present disclosure illustrate embodiments of the heat exchange system of the present invention, and it is obvious that the scope of the present invention is not limited to the scope of FIGS. 2 to 11.
  • In the heat exchange system shown in FIG. 2, the heat exchange part is composed for heat exchanging the first high temperature stream with the third low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the second low temperature stream, and heat exchanging the fifth high temperature stream with the fourth low temperature stream.
  • In the heat exchange system shown in FIG. 3, the heat exchange part is composed for heat exchanging the first high temperature stream with the second low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the third low temperature stream, and heat exchanging the fifth high temperature stream with the fourth low temperature stream.
  • In the heat exchange system shown in FIG. 4, the heat exchange part is composed for heat exchanging the first high temperature stream with the second low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the fourth low temperature stream, and heat exchanging the fifth high temperature stream with the third low temperature stream.
  • In the heat exchange system shown in FIG. 5, the heat exchange part is composed for heat exchanging the first high temperature stream with the second low temperature stream and the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, and heat exchanging the fourth high temperature stream with the third low temperature stream.
  • In the heat exchange system shown in FIG. 6, the heat exchange part is composed for heat exchanging the first high temperature stream with the second low temperature stream and the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, and heat exchanging the fifth high temperature stream with the third low temperature stream.
  • In the heat exchange system shown in FIG. 7, the heat exchange part is composed for heat exchanging the first high temperature stream with the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the third low temperature stream, and heat exchanging the fifth high temperature stream with the second low temperature stream.
  • In the heat exchange system shown in FIG. 8, the heat exchange part is composed for heat exchanging the first high temperature stream with the third low temperature stream and the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the third low temperature stream, and heat exchanging the fifth high temperature stream with the second low temperature stream.
  • In the heat exchange system shown in FIG. 9, the heat exchange part is composed for heat exchanging the first high temperature stream with the fourth low temperature stream, heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, heat exchanging the fourth high temperature stream with the second low temperature stream, and heat exchanging the fifth high temperature stream with the third low temperature stream.
  • In the heat exchange system shown in FIG. 10, the heat exchange part is composed for heat exchanging the first high temperature stream and the second high temperature stream with the first low temperature stream, heat exchanging the third high temperature stream with the fourth low temperature stream, heat exchanging the fourth high temperature stream with the second low temperature stream, and heat exchanging the fifth high temperature stream with the third low temperature stream.
  • In the heat exchange system shown in FIG. 11, the heat exchange part is composed for heat exchanging the first high temperature stream and the second high temperature stream with the first low temperature stream, heat exchanging the third high temperature stream with the fourth low temperature stream, heat exchanging the fourth high temperature stream with the third low temperature stream, and heat exchanging the fifth high temperature stream with the second low temperature stream.
    • EXPLANATION OF SYMBOLS
    • 11: first alcohol tank
    • 12: second alcohol tank
    • 101: first alcohol stream
    • 102: second alcohol stream (second low temperature stream)
    • 21: reaction part
    • 211: first reaction product stream
    • 22: trans reaction part
    • 221: second reaction product stream (third high temperature stream)
    • 3: preliminary purification part
    • 301: purified product stream (fourth high temperature stream)
    • 302: purified product stream
    • 303: unreacted first alcohol stream (second high temperature stream)
    • 41: first washing part
    • 411: first neutralized product stream (third low temperature stream)
    • 42: second washing part
    • 421: second neutralized product stream (first low temperature stream)
    • 51: first purification part
    • 511: first diester-based composition stream
    • 512: unreacted first alcohol stream
    • 52: second purification part
    • 521: second diester-based composition stream
    • 522: unreacted mixed alcohol stream (first high temperature stream)
    • 61: mixed alcohol tank
    • 611: mixed alcohol stream (fourth low temperature stream)
    • 62: separation part
    • 621: first alcohol stream (fifth high temperature stream)
    • 622: second alcohol stream

Claims (14)

  1. A heat exchange system in a preparation system of a diester-based composition, the preparation system comprising:
    a first alcohol tank for storing and injecting a first alcohol;
    a second alcohol tank for storing and injecting a second alcohol;
    a reaction part for performing esterification reaction of the first alcohol and a dicarboxylic acid to produce a first reaction product;
    a preliminary purification part for removing an unreacted first alcohol in the first reaction product to produce a purified product;
    a trans reaction part for performing trans esterification reaction of the purified product and the second alcohol to obtain a second reaction product;
    a first washing part for neutralizing and washing the purified product to obtain a first neutralized product;
    a second washing part for neutralizing and washing the second reaction product to obtain a second neutralized product;
    a first purification part for removing an unreacted first alcohol in the first neutralized product and injecting the removed unreacted first alcohol into the first alcohol tank and obtaining a remaining first diester-based composition;
    a second purification part for removing a mixed alcohol of an unreacted first alcohol and second alcohol in the second neutralized product and injecting the removed mixed alcohol into a mixed alcohol tank and obtaining a remaining second diester-based composition;
    the mixed alcohol tank for cooling and storing the mixed alcohol; and
    a separation part for separating the mixed alcohol into a first alcohol and a second alcohol and injecting thereof into at least one among the first alcohol tank and the reaction part, and the second alcohol tank, respectively, wherein
    the heat exchange system comprises a heat exchange part composed for heat exchange between:
    one or more high temperature streams selected from the group consisting of a first high temperature stream discharged from the second purification part and injected into the mixed alcohol tank, a second high temperature stream discharged from the preliminary purification part and injected into the first alcohol tank, a third high temperature stream discharged from the trans reaction part and injected into the second washing part, a fourth high temperature stream discharged from the preliminary purification part and injected into the first washing part, and a fifth high temperature stream discharged from the separation part and injected into the first alcohol tank, and
    one or more low temperature streams selected from the group consisting of a first low temperature stream discharged from the second washing part and injected into the second purification part, a second low temperature stream discharged from the second alcohol tank and injected into the trans reaction part, a third low temperature stream discharged from the first washing part and injected into the first purification part, and a fourth low temperature stream discharged from the mixed alcohol tank and injected into the separation part.
  2. The heat exchange system according to claim 1, wherein the heat exchange part is composed for heat exchanging selected one high temperature stream with selected multiple low temperature streams.
  3. The heat exchange system according to claim 1, wherein the heat exchange part is composed for heat exchanging selected multiple high temperature streams with selected one low temperature stream.
  4. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream with the third low temperature stream,
    heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream,
    heat exchanging the fourth high temperature stream with the second low temperature stream, and
    heat exchanging the fifth high temperature stream with the fourth low temperature stream.
  5. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream with the second low temperature stream,
    heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream,
    heat exchanging the fourth high temperature stream with the third low temperature stream, and
    heat exchanging the fifth high temperature stream with the fourth low temperature stream.
  6. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream with the second low temperature stream,
    heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream,
    heat exchanging the fourth high temperature stream with the fourth low temperature stream, and
    heat exchanging the fifth high temperature stream with the third low temperature stream.
  7. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream with the second low temperature stream and the fourth low temperature stream,
    heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, and
    heat exchanging the fourth high temperature stream with the third low temperature stream.
  8. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream with the second low temperature stream and the fourth low temperature stream,
    heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream, and
    heat exchanging the fifth high temperature stream with the third low temperature stream.
  9. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream with the fourth low temperature stream,
    heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream,
    heat exchanging the fourth high temperature stream with the third low temperature stream, and
    heat exchanging the fifth high temperature stream with the second low temperature stream.
  10. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream with the third low temperature stream and the fourth low temperature stream,
    heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream,
    heat exchanging the fourth high temperature stream with the third low temperature stream, and
    heat exchanging the fifth high temperature stream with the second low temperature stream.
  11. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream with the fourth low temperature stream,
    heat exchanging the second high temperature stream and the third high temperature stream with the first low temperature stream,
    heat exchanging the fourth high temperature stream with the second low temperature stream, and
    heat exchanging the fifth high temperature stream with the third low temperature stream.
  12. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream and the second high temperature stream with the first low temperature stream,
    heat exchanging the third high temperature stream with the fourth low temperature stream,
    heat exchanging the fourth high temperature stream with the second low temperature stream, and
    heat exchanging the fifth high temperature stream with the third low temperature stream.
  13. The heat exchange system according to claim 1, wherein the heat exchange part is composed for
    heat exchanging the first high temperature stream and the second high temperature stream with the first low temperature stream,
    heat exchanging the third high temperature stream with the fourth low temperature stream,
    heat exchanging the fourth high temperature stream with the third low temperature stream, and
    heat exchanging the fifth high temperature stream with the second low temperature stream.
  14. A preparation system of a diester-based composition, comprising the heat exchange system according to any one of claim 1 to claim 13.
EP20835106.4A 2019-07-04 2020-07-02 Heat exchange system and preparation system of diester-based composition comprising the same Active EP3995484B1 (en)

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KR1020190080463A KR102489173B1 (en) 2019-07-04 2019-07-04 System for Heat Exchange and System for Manufacturing Di-ester based Composition Comprising the Same
PCT/KR2020/008682 WO2021002707A1 (en) 2019-07-04 2020-07-02 Heat exchange system and diester-based composition preparation system comprising same

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KR102489172B1 (en) * 2019-07-04 2023-01-18 주식회사 엘지화학 Manufacturing unit of diester-based material and method of manufacturing the same

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JP2022535230A (en) 2022-08-05
EP3995484A4 (en) 2022-09-07
EP3995484B1 (en) 2023-04-26
KR102489173B1 (en) 2023-01-18
CN113710639A (en) 2021-11-26
KR20210004277A (en) 2021-01-13
WO2021002707A1 (en) 2021-01-07
JP7314449B2 (en) 2023-07-26
CN113710639B (en) 2023-07-18
US20220203323A1 (en) 2022-06-30

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